Atomic control of active-site ensembles in ordered alloys to enhance hydrogenation selectivity

Anish Dasgupta, Haoran He, Rushi Gong, Shun Li Shang, Eric K. Zimmerer, Randall J. Meyer, Zi Kui Liu, Michael J. Janik, Robert M. Rioux

Research output: Contribution to journalArticlepeer-review

48 Scopus citations

Abstract

Intermetallic compounds offer unique opportunities for atom-by-atom manipulation of catalytic ensembles through precise stoichiometric control. The (Pd, M, Zn) γ-brass phase enables the controlled synthesis of Pd–M–Pd catalytic sites (M = Zn, Pd, Cu, Ag and Au) isolated in an inert Zn matrix. These multi-atom heteronuclear active sites are catalytically distinct from Pd single atoms and fully coordinated Pd. Here we quantify the unexpectedly large effect that active-site composition (that is, identity of the M atom in Pd–M–Pd sites) has on ethylene selectivity during acetylene semihydrogenation. Subtle stoichiometric control demonstrates that Pd–Pd–Pd sites are active for ethylene hydrogenation, whereas Pd–Zn–Pd sites show no measurable ethylene-to-ethane conversion. Agreement between experimental and density-functional-theory-predicted activities and selectivities demonstrates precise control of Pd–M–Pd active-site composition. This work demonstrates that the diversity and well-defined structure of intermetallics can be used to design active sites assembled with atomic-level precision. [Figure not available: see fulltext.]

Original languageEnglish (US)
Pages (from-to)523-529
Number of pages7
JournalNature Chemistry
Volume14
Issue number5
DOIs
StatePublished - May 2022

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • General Chemical Engineering

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